The invention relates to (per)halogenated polyorganosiloxanes (POS) derived from (per)halogenated olefins (e.g. .alpha.-olefins) by means of a hydrosilylation reaction, it also being possible to present said reaction as the addition of a hydrogenated silicon compound onto a halogenated reactant having one or more ethylenic or alkynylic units of unsaturation.
It is known in particular that the effects of fluorination, and more precisely of the introduction of perfluorinated units into polymers, are:
to lower the surface energies, PA1 to improve the thermal and chemical stability and PA1 to impart organophobicity and oleophobicity properties. PA1 a+b+p=3; a=2 or3; b, p=0 or 1; PA1 z is between 0 and 200, preferably between 1 and 90; PA1 y.sub.1 is between 0 and 10, preferably between 0 and 5; PA1 y is between 0 and 50, preferably between 0 and 25; and PA1 e is between 1 and 200, preferably between 1 and 90, PA1 with the provisos that: PA1 .DELTA. if z.noteq.0, then5.ltoreq.z+y.sub.1 +y+e&lt;200, preferably 10.ltoreq.z+y.sub.1 +y+e.ltoreq.100 and [z/(z+y+y.sub.1 +e+2)].100.gtoreq.3, preferably 5; PA1 .DELTA. if z=0, then 5.ltoreq.y+y.sub.1 +e.ltoreq.100, b being other than 0 in at least one of the monovalent terminal siloxy units M; PA1 .DELTA. if e.noteq.0, then 5.ltoreq.z+y.sub.1 +y+e.ltoreq.200, preferably 10.ltoreq.z+y.sub.1 +y+e.ltoreq.100 and [z/(z+y+y.sub.1 +e+2)].100.gtoreq.3, preferably 5; and PA1 .DELTA. if e=0, then 5.ltoreq.y+y.sub.1 +z.ltoreq.100, p being other than 0 in at least one of the units M; PA1 1.ltoreq.z' .ltoreq.9, preferably 1.ltoreq.z'.ltoreq.4.5; PA1 0.ltoreq.y'.sub.1.ltoreq.0.5, preferably 0.ltoreq.Y'.sub.1.ltoreq.0.25; PA1 0.ltoreq.y'.ltoreq.5, preferably 0.ltoreq.y'.ltoreq.0.5; PA1 each radical R.sup.1, R.sup.2 on the one hand is identical to or different from like radicals of the same exponent and the other radical of different exponent, and on the other hand is a linear or branched C.sub.1 -C.sub.12 --(cyclo)alkyl--preferably C.sub.1 -C.sub.6 --(cyclo)alkyl--group, an aryl, an aralkyl or an alkylaryl, these groups optionally being substituted; PA1 Gf is an optionally halogenated--preferably (per)fluorinated--functional monovalent radical of identical or different type in the z or z' siloxy units D and/or the two siloxy units M in which it is present, and having the following average formula: ##STR3## PA1 .DELTA. where h=0 or 1; g=0 or 1; j=0 or 1 and k=1 or 2; PA1 .DELTA. with the proviso that at least one radical Gf is present in said POS (I) or (II), the radicals Gf preferably being present to the extent of at least 60 mol %; PA1 .DELTA. Z.sub.1 being a divalent radical of the formula EQU .paren open-st.C.sub.m H.sub.2m.paren close-st. PA1 .DELTA.Z.sub.2 being a mono-, di- or tri-valent radical of the formula ##STR4## PA1 one or both of the free valences of the carbonyl(s) being joined to --Z.sub.3 Rf and, in the case where only one of said free valences is joined to --Z.sub.3 Rf, the other then being joined to a hydroxyl; ##STR5## PA1 at least one of the free valences of the carbonyls being joined to --Z.sub.3 --Rf and, in the case where only one of these free valences is joined to --Z.sub.3 --Rf, the other then being joined to a linear or branched C.sub.1 -C.sub.6 -alkoxy; and PA1 R.sup.a =H, aryl or linear or branched C.sub.1 -C.sub.6 -lower alkyl, preferably CH.sub.3 ; ##STR6## PA1 h=0 in Gf; PA1 one or both of the free valences of the carbonyl(s) being joined to --Z.sub.3 -- Rf and, in the case where only one of said free valences is joined to --Z.sub.3 Rf, the other then being joined to a hydroxyl or to a linear or branched C.sub.1 -C.sub.6 -alkoxy; ##STR7## PA1 one or both of the two free valences other than the valence .rect-solid. being joined to --Z.sub.3 --Rf and, in the case where only one of these two valences is joined to --Z.sub.3 --Rf, the other then being joined to OH or to a linear or branched C.sub.1 -C.sub.6 -alkoxy; or ##STR8## PA1 one or both of the two free valences other than the valence .rect-solid. being joined to --Z.sub.3 --Rf and, in the case where only one of these two valences is joined to --Z.sub.3 --Rf, the other then being joined to OH or to a linear or branched C.sub.1 -C.sub.6 -alkoxy; PA1 R.sup.b =H or linear or branched C.sub.1 -C.sub.6 -lower alkyl, methyl being preferred; PA1 .DELTA. Z.sub.3 is a divalent radical of the formula EQU .rect-solid.U--C.sub.n H.sub.2n -- PA1 where n.gtoreq.1 and U=O, S, NH or NHSO.sub.2, preferably O; and PA1 .DELTA. Rf being a perhalogenated--preferably perfluorinated--radical and particularly preferably a linear or branched perfluoroalkyl radical having one of the following formulae: ##STR9## PA1 E is a monovalent functional radical, other than Gf defined above, of identical or different type in the e or e' siloxy units D and/or the two siloxy units M in which it is present, and preferably chosen from the groups having at least one of the following functional groups E.sub.1 to E.sub.13 : PA1 .DELTA. E.sub.1 = EQU .rect-solid.(Z.sub.1).sub.b=0,1.sup.-- (Z.sub.2).sub.g=o,1.sup.-- PA1 Z.sub.1 is defined in the same way as given above for Gf where m.gtoreq.2; and PA1 Z.sub.2 corresponds to: ##STR10## PA1 where at least one of the free valences of a carbonyl is bonded to an OH, or else these two free valences are both joined to the same oxygen atom; ##STR11## PA1 where the two free valences of the carbonyls are each bonded to a linear or branched C.sub.1 -C.sub.6 -alkoxy; ##STR12## PA1 the free valence of the carbonyl being joined to a linear or branched C.sub.1 -C.sub.6 -alkoxy or else to an OH; ##STR13## PA1 where at least one of the free valences of a carbonyl is bonded to an OH or a linear or branched C.sub.1 -C.sub.6 -alkoxy, or else these two free valences are both joined to the same oxygen atom; ##STR14## PA1 one or both of the two free valences other than the valence .rect-solid. being joined to Z.sub.3 --Rf and, in the case where only one of these two valences is joined to Z.sub.3 --Rf, the other then being joined to OH or to a linear or branched C.sub.1 -C.sub.6 -alkoxy; or ##STR15## PA1 Z.sub.1 and Z.sub.2 being identical to or different from their counterparts present in Gf and described above; and PA1 W being as defined above for Gf; and PA1 .DELTA.E.sub.2 =amine; E.sub.3 =alkoxy; E.sub.4 =acyl; E.sub.5 =acyloxy; E.sub.6 =hydroxyl; PA1 E.sub.7 =trialkoxysilyl; E.sub.8 =amide; E.sub.9 =ester; E.sub.10 =phenol; E.sub.11 =arylalkoxy; E.sub.12 =aryloxy; E.sub.13 =ether-hydroxy. PA1 those with an alkylene linkage --(C.sub.m H.sub.2m)-- where m.gtoreq.2; PA1 those with an alkylene linkage (C.sub.m H.sub.2m).sub.m+2 (m.gtoreq.0) extended by a divalent or trivalent hydrocarbon radical W devoid of an ether --O--, and having one or more perfluorinated radicals Rf; PA1 those with an alkylene linkage (C.sub.m H.sub.2m).sub.m (m&gt;2) extended either by W .omega.-hydroxylated and alkoxylated by a radical whose free end is Rf, or by W alkoxylated by two radicals carrying Rf; PA1 those with an alkylene linkage --(C.sub.m H.sub.2m)-- (m&gt;0) extended by a divalent or trivalent radical belonging to the general family of the radicals W and joined to or forming part of a cyclic unit whose free valence(s), other than that joined to Si, bonds (bond) with any radical(s) Z.sub.3 Rf and/or with alkyl, alkoxy or hydroxyl substituents; PA1 those with an alkylene linkage --(C.sub.m H.sub.2m)-- (m&gt;0) extended by a trivalent silyl radical in which the free valences, other than that joined to Si, bond with any radical(s) Z.sub.3 Rf and/or with alkyl, alkoxy or hydroxyl substituents; and finally PA1 those with a linkage not containing a divalent alkylene radical (h=0) but having a radical W directly connected to Si, and also carrying at least one radical Rf. PA1 an epoxy-functional group El preferably selected from the following groups: PA1 and/or an isocyanate group El preferably selected from the following groups: ##STR17## PA1 and/or an amino-functional group E.sub.2 preferably selected: PA1 or from secondary or tertiary amine groups forming part of a cyclic hydrocarbon chain (hals), of the formula: ##STR18## PA1 .gradient. the radicals R.sup.20, which are identical to or different from one another, are selected from linear or branched alkyl radicals having from 1 to 3 carbon atoms, phenyl radicals and benzyl radicals; PA1 .gradient. R.sup.21 is selected from a hydrogen atom, linear or branched alkyl radicals having from 1 to 12 carbon atoms, alkylcarbonyl radicals in which the alkyl radical is a linear or branched radical having from 1 to 8 carbon atoms, phenyl and benzyl radicals and a radical O; PA1 .gradient. t is a number selected from 0 and 1; PA1 .gradient. the preferred radicals R.sup.20 being methyls, the radical R.sup.21 being a hydrogen atom or a methyl radical and t advantageously being a number equal to 1; and/or PA1 .gradient. a hydroxy-functional group E.sub.6 preferably selected from the following groups: 3-hydroxypropyl and 3-(2-hydroxyethoxy)propyl. PA1 Gf corresponds to the definition given above where h=g=1 or h=1 and g=0; PA1 E=E.sub.1 to E.sub.13 ; PA1 R.sup.1 and R.sup.2 are as defined above, preferably methyl, propyl or butyl; PA1 c1+d1=3 and preferably c1=2, d1=1; PA1 c2+d2=3 and preferably c2=2, d2=1; PA1 1.ltoreq.z.ltoreq.90, preferably 1.ltoreq.z.ltoreq.50; PA1 1.ltoreq.e.ltoreq.100, preferably 1.ltoreq.e.ltoreq.60; PA1 0.ltoreq.y.sub.1.ltoreq.10, preferably 0.ltoreq.y.sub.1.ltoreq.5; PA1 0.ltoreq.y.ltoreq.50, preferably 0.ltoreq.y.ltoreq.25. PA1 h=1 m.gtoreq.0, g=1, j=0 or 1 and k=1; PA1 R.sup.3 =H or C.sub.1 -C.sub.6 -alkyl; PA1 R.sup.4 and R.sup.5 are identical to or different from one another and correspond to --(CH.sub.2)--.sub.u.gtoreq. 0; and PA1 R.sup.6 and R.sup.7 are identical to or different from one another and are Z.sub.3 --Rf, where Z.sub.3 =--O--(CH.sub.2)--.sub.s, s being between 0 and 10, at least one of these two radicals R.sup.6 and R.sup.7 corresponding to Z.sub.3 --Rf; ##STR24## PA1 h=0 or 1, m.gtoreq.0, g=1, i=2 to 10, j=1 and k=1; and PA1 R.sup.6 and R.sup.7 are as defined above; ##STR26## PA1 h=1, m.gtoreq.0, g=1, i=2 to10,j=0 or 1 and k=1; and PA1 R.sup.6 is as defined above; and PA1 where: PA1 .smallcircle. R.sup.a and R.sup.9 independently are H or linear or branched C.sub.1 -C.sub.6 -lower alkyl, preferably CH.sub.3 ; PA1 .smallcircle. R.sup.10 and R.sup.11 independently are OH, linear or branched C.sub.1 -C.sub.6 -alkoxy or Z.sub.3 --Rf, at least one of the radicals R.sup.10 and R.sup.11 being --Z.sub.3 Rf; and PA1 .smallcircle. i=0 to 10, preferably 0 to 3 and particularly preferably 1; ##STR28## PA1 A) at least one polyalkylhydrogenosiloxane--preferably polymethylhydrogenosiloxane--oil PA1 B) with at least one (per)halogenated--preferably (per)fluorinated--olefin which is a precursor of Gf and has the formula (Gf,): EQU Z.sub.1P Rf PA1 Z.sub.1p =olefinic precursor of Z.sub.1 and PA1 Rf is as defined above, PA1 Z.sub.1p =olefinic precursor of Z.sub.1 and PA1 Z.sub.2p =olefinic precursor of Z.sub.2, PA1 the reaction product A+C optionally being brought into contact with a reactant of the type Z.sub.3p Rf, where Z.sub.3p is a precursor of Z.sub.3 and Rf is as defined above, to give grafts Gf=--Z.sub.1 Rf and/or --Z.sub.1 Z.sub.2 Z.sub.3 Rf, PA1 Z.sub.1p is the olefliuc precursor of the radical Z.sub.1, as defined above, and PA1 Z.sub.2, Z.sub.3, Rf, h, g, j and k are also as defined above, PA1 with the proviso that if h=0, then g=1 and Z.sub.2 becomes an olefinic precursor Z.sub.2p, PA1 linear POS such as polymethylhydrogenosiloxanes, especially those of the type: PA1 Me.sub.3 SiO(SiMe.sub.2 O)--.sub.8 (SiHMeO)--.sub.4 SiMe.sub.3 PA1 Me.sub.3 SiO(SiMeHO)--.sub.50 SiMe.sub.3 PA1 at least one POS as defined above or obtained by the process as defined above; PA1 water; and PA1 at least one surfactant. PA1 ethoxylated fatty alcohols PA1 ethoxylated alkylphenols PA1 ethoxylated alkylamine salts PA1 ethoxylated polyalcohols PA1 alkylammonium salts, etc. PA1 lubricants, PA1 agents for lowering surface tension, PA1 dirt repellents, PA1 antiadhesives, PA1 antifoams, PA1 oleophobic and/or hydrophobic agents, PA1 raw materials for the production of elastomers for resisting chemical attack and solvents, and PA1 raw materials for the preparation of a film and/or coating possessing at least one of the above-mentioned properties. PA1 at least one POS as defined above or obtained by the process as defined above, PA1 and/or at least one emulsion as defined above, PA1 said POS used preferably carrying:
This type of functionalization by halogenation, and in particular by perfluorination, has been applied to silicone polymers, particularly of the cyclic or non-cyclic polyorganosiloxane type, since the 1970s.
Silicone oils grafted by fluorinated units are thus available which have applications in the textile field as stain or dirt repellents or which can be used as lubricants, as antiadhesives specific for certain adhesives (silicones of high adhesive strength), as grease repellents or else as antifoams. Fluorinated silicone fluids can also be formulated with different thickeners to form mastics or any other sealing and/or jointing materials.
In crosslinked form these fluorinated silicones can be shaped into a variety of engineering parts by molding or extrusion.
For further details on these fluorinated silicones, reference may be made to the article by OGDEN R. PIERCE entitled "Fluorosilicones"--1970--John Wiley & Sons Inc., pages 1 to 15.
A first known strategy for the industrial synthesis of silicones containing perfluorinated units includes "hydrosilylating" a dihalogenohydrogenoorganosilane, such as MeHSiCl.sub.2 (Me=methyl), with an unsaturated compound carrying a perfluorinated unit and having the general formula CH.sub.2 =CH--Rf (Rf=perfluorinated unit). The addition of the silane onto this olefin yields a perfluorinated dihalogenoorganosilane, which can be hydrolyzed to produce a functionalized silicone; this can be a cyclic tetramer, for example. It is possible to subject the latter to a redistribution reaction to give a perfluorinated linear polyorganosiloxane (POS). The hydrosilylation reactions which are involved in this kind of synthesis, and which use various combinations of silicone hybrids and perfluorinated olefins, are known to be catalyzed by selected metal compounds, particularly certain group VIII metals such as platinum. Pt/Sn complexes have thus been employed as hydrosilylation catalysts--cf patent U.S. Pat. No. 4,089,882 (SHINETSU). This synthetic strategy appears to be relatively complex and hence expensive.
With a view to industrial simplification, a second synthetic strategy has been proposed which is based on the direct hydrosilylation of a silicone containing SiH units with an .alpha.-fluorinated olefin, e.g. of the type CH.sub.2 =CH--Rf, this perfluorinated unit Rf being attached directly to the olefinic CH by a carbon atom carrying at least one fluorine atom. Here again a variety of group VIII metal catalysts, in particular those based on platinum, are used in this hydrosilylation reaction. It has been found, however, that these catalysts do not afford very high yields. In particular, the conventional industrial hydrosilylation catalysts based on platinum (for example of the KARSTEDT type) are not very efficient. Moreover, it has been observed that substantial amounts of by-product are generated, obviously to the detriment of the perfluorination of the silicones. In these known perfluorinated POS, the radical Rf is joined directly to the Si of the silicone chain. In other words, the linkage in this case corresponds to --CH.sub.2 --CH.sub.2 --(CH.sub.2)--.sub.m where m=0.
It is these linkages which are used in U.S. Pat. No. 5,233,071. They originate from the hydrosilylation of a-olefins. However, to overcome the deficiencies of the hydrosilylation catalysts used in the prior art, the process described in said patent involves cobalt-based organometallic complexes [(Co.sub.2 CO.sub.8, Co.sub.2 CO.sub.6)(PR.sub.3).sub.3, where R=alkyl, aryl]. Such a technical proposal has appeared unsatisfactory because the reaction times obtained are of the order of a few days and it is essential to use a substantial amount of catalyst (1-2%), which is particularly unfavorable in terms of the economics of the process.
One appreciable disadvantage of these cobalt-based complexes is that they catalyze reactions other than hydrosilylation. In particular, they are capable of taking part in polymerization processes involving the rupture of epoxy rings. This lack of specificity is particularly troublesome. Moreover, these are not industrial catalysts.
U.S. Pat. No. 5,348,769 discloses linear or cyclic polyorganosiloxanes comprising siloxy units D substituted by a first perfluorinated functional unit of the formula --R.sup.3 ZRf, and other siloxy units D carrying a second functional unit of the ether-hydroxyl or alkyl-hydroxyl type. The linkage or bridge joining Si to Rf in the first perfluorinated functional unit consists especially of --(CH.sub.2).sub.x Z, where x=2, 3 or 4 and Z=NHCO, NHSO.sub.2, O.sub.2 C, O.sub.3 S, OCH.sub.2 CH.sub.3, NHCH.sub.2 CH.sub.2 or CH.sub.2 CHOHCH.sub.2. The catalyst used is preferably chloroplatinic acid. This is not one of the simplest techniques as it requires the prior preparation of the perfluoroalkylated olefinic reactant. This considerably lengthens the synthesis times and hence increases the cost of the process.
Apart from these linkages whose precursors are perfluoroalkylated .alpha.-olefins of the formula CH.sub.2 =CH--Rf, the technical literature of the prior art also describes bridges whose olefinic precursors are of the type CH.sub.2 =CH)--L--Rf, the chemical bond between L and Rf being an ester bond. The latter results from the reaction of a carboxyl group with a perhalogenated alcohol, preferably perfluorinated alcohol, and said carboxyl group is generally the hydrolysis product of an acid anhydride.
Thus PCT patent application WO 94/12561 discloses POS grafted by fluorinated units only in the .alpha. and .omega. positions at the ends of the silicone chains. These POS .alpha.,.omega.-perfluorinated on alkyl ester groups do not exhibit optimum properties in respect of surface tension lowering or oleophobicity and hydrophobicity.
European patent application No. 0 640 644 describes perfluorinated (Rf) silicone derivatives which can be used in cosmetic formulations. These perfluorinated silicone derivatives are characterized by siloxy units D carrying three different types of perfluorinated grafts, namely: ##STR1##
where R.sup.2, R.sup.3 =alkyl, e.g. CH.sub.3 ;
2.ltoreq.i.ltoreq.16, e.g. i=3; 1.ltoreq.m,n.ltoreq.6; .ltoreq.p.ltoreq.200; 0.ltoreq.r.ltoreq.50; PA0 the number of siloxy units D grafted in this way is between 1 and 200; and PA0 X, Y=single bond, --CO-- or C.sub.1 --C.sub.6 -alkylene. PA0 C) and/or with at least one (per)halogenated--preferably (per)fluorinated--olefin of the formula Z.sub.1p Z.sub.2p, PA0 D) in the presence of an effective amount of a metal hydrosilylation catalyst preferably based on platinum, PA0 E) and finally with a reactant E, formed by an olefinic precursor of E, E.sub.p being capable of hydrosilylation by the .tbd.SiH of the POS in the presence of D. PA0 A) at least one polyalkylhydrogenosiloxane--preferably polymethylhydrogenosiloxane--oil PA0 F) with at least one halogenated--preferably (per)fluorinated--olefin which is a precursor of Gf and has the formula (Gf.sub.p): EQU (Z.sub.1p).sub.h --(Z.sub.s).sub.8.brket open-st.(Z.sub.3).sub.j --Rf].sub.k PA0 G) and/or with at least one olefinic precursor E.sub.p of E, PA0 D) in the presence of an effective amount of a metal hydrosilylation catalyst preferably based on platinum.
A common feature of these perfluorinated grafts (1) to (3) is the presence of ether bonds within the linkage joining the perfluorinated radical Rf to the silicon. Each of these ether bonds represents a possible point of rupture by chemical attack, under certain conditions.
This is a major disadvantage of these known perfluorinated POS because the labile character of the perfluorinated groups is clearly unacceptable in certain applications.
This review of the prior art shows that there are no chemically stable, halogenated--preferably (per)fluorinated--POS which comprise on the one hand fluorinated lateral grafts resulting from the hydrosilylation of perfluorinated olefins with SiH units and having alkyl and/or alkyl ester linkages but not ether linkages, and on the other hand other, non-perfluorinated functional units capable of giving them diverse and varied physical and chemical properties and opening up avenues in numerous applications.
Furthermore, the prior art contains even fewer disclosures of such POS which can be obtained in a simple, economic and hence perfectly industrial manner.